KR20160020484A - Method for producing aliphatic or partially aromatic polyamides, said method comprising a solid-phase polymerization process - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a process for producing an aliphatic or semiaromatic polyamide in which a polyamide prepolymer is solid-state polymerized.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for producing aliphatic or partially aromatic polyamides,

TECHNICAL FIELD The present invention relates to a process for producing an aliphatic or semiaromatic polyamide in which a polyamide prepolymer is solid-state polymerized.

Polyamides are one of the polymers that are produced on a large scale worldwide and are useful for many additional end uses besides the main fields of application in films, fibers and materials. Among polyamides, polyamido-6- (polycaprolactam) and polyamide-6,6 (nylon, polyhexamethyleneadipamide) are polymers produced in the maximum amount. Polyamide-6,6 is prepared by the polycondensation of an aqueous solution comprising a so-called AH salt solution, namely adipic acid and 1,6-diaminohexane (hexamethylenediamine), in a stoichiometric amount. The conventional method for producing polyamide-6 is the hydrolytic ring-opening polymerization of? -Caprolactam, and still has a very large industrial importance. Conventional production processes for polyamide-6 and polyamide-6,6 are described, for example, in Kunststoffhandbuch, 3/4 Technische Thermoplaste: Polyamide [Plastics Handbook, 3/4 Industrial Thermoplastics: Polyamides], Carl Hanser Verlag, 1998 , Munich, p. 42-71.

A further important group of polyamides is the group of semi-crystalline or amorphous thermoplastic semi-aromatic polyamides, and these polyamides are important industrial plastics for a wide range of applications. They are notable for their high temperature stability, and are also referred to as high temperature polyamides (HTPA). An important area for the use of HTPA is the production of electrical and electronic components, and polymers suitable for use in soldering operations (lead-free soldering) under lead-free conditions are, in particular, polyphthalamide (PPA) based polymers. HTPA is particularly useful for manufacturing plug connectors, microswitches and micro button and semiconductor components, for example, the reflector housings of light emitting diodes (LEDs). A further important area of application for HTPA is high temperature automotive applications. Important properties here are good thermal aging resistance of the polymers used, and high strength and toughness and weld line strength. The amorphous HTPA or HTPA with very low crystalline content is transparent and is particularly suitable for applications where transparency is favored. Semi-crystalline HTPA is generally noted for long term stability at high ambient temperatures, and is suitable, for example, for applications in engine room areas.

The preparation of the semi-aromatic polyamides is generally carried out in an aqueous salt solution from one or more diamines and one or more dicarboxylic acids and optionally further monomer components, for example lactam, omega-amino acids, monoamines, monocarboxylic acids and mixtures thereof With the proviso that at least one of the components has an aromatic group. After formation of the salt solution, oligomerization into the liquid phase continues, during which time water is generally still not removed. At the end of this oligomerization, the oligomer has an average of, for example, 4 to 10 repeating units. In order to further increase the molecular weight, the following two separate routes are available. In a first variant, the oligomer formed is converted into a solid by dehydration and is subjected to so-called solid state polymerization (SSP). In a second variant, water is removed in a controlled manner and the temperature is increased to convert the aqueous solution to a melt for further polycondensation. Upon completion of the polymerization to the melt or solid phase, a prepolymer having a number average molecular weight of about 500 to 12000 g / mol is obtained.

European Patent Application No. 0 693 515 A1 describes a process for preparing precondensates of semi-crystalline or amorphous, thermoplastic processible semi-aromatic polyamides in a multistage batch operation comprising the following steps a) to e) It has:

(a) a salt forming phase for the preparation of the salt (s) from the diamine (s) and the dicarboxylic acid (s) and optionally a portion providing a low molecular weight oligomer at a temperature of 120 ° C. to 220 ° C. and a pressure of 23 bar or less. Prereaction,

b) optionally transferring the solution from step a) to a second reaction vessel or stirred autoclave under conditions present at the end of the preparation of the solution,

c) heating the reactor contents to the furnace temperature and converting to a precondensate via controlled adjustment of the partial steam pressure to a given value, which is maintained by controlled introduction of steam from the steam generator optionally connected to the autoclave, In this accelerated reaction phase,

d) a stationary phase which must be maintained for at least 10 minutes in the process of setting the temperature of the reactor contents and the partial steam pressure to values determined for the movement of the precondensate in the downstream processing stage, respectively,

In the case of a total condensate of semi-crystalline (co) polyamides having a melting point above 280 ° C, the temperature of the reactor contents during phases c) and d) must not exceed 265 ° C, in particular the temperature of the reactor contents and the amide (Co) polyamides during phases c) and d), and more preferably, on the basis of the difference between the minimum partial vapor pressure P _H2O

e) Exhaust phase which can be fed into the final reactor immediately after the molten state has passed the condensation or in the solid state and optionally further processing steps.

In order to obtain a predetermined high molecular weight, polycondensation is generally carried out for the prepolymer. Regarding this polycondensation, European Patent Application No. 0 693 515 A1 does not contain specific details. The polycondensation in the above-mentioned continuous extruder is possible only when the prior art is known.

DE 41 42 978 describes a multilayer composite system for reusable packaging materials consisting of one or more copolyamide protective layers and one or more layers of copolyamide barrier layers, . According to an embodiment, the copolyamide is made into a melt in a pressure autoclave while spraying nitrogen. There is no description about the polycondensation to the solid phase.

International Patent Application Publication No. 2004/055084, at least to a monomer or a condensate before: a) terephthalic acid, b) at least one carbon atom less than 44 dimerized fatty acid, and c) the formula _{H 2 N- (CH 2) X} - Thermoplastic processible semiaromatic copolyamides prepared by condensation of one or more aliphatic diamines of the formula NH ₂ (x being an integer from 4 to 18). For the preparation of copolyamides, only known methods are generally referred to. In the examples, post condensation is carried out with the melt in an autoclave for all condensates. There is no disclosure of the use of inert gases during post condensation.

U.S. Patent Application No. 2003/0176624 Al describes a process for solid phase drying or solid state polymerization of polyamides based on xylylenediamine. This solid phase polymerization takes place in an inert gas stream or under reduced pressure.

International Patent Application Publication No. 2007/048728 describes polyamides formed from adipic acid and m-xylylenediamine having an amino end group content of less than 15 mmol / kg. The prepolymer is first prepared, which can be optionally extracted and solid-phase condensed. Solid-phase condensation can be carried out under reduced pressure or under an inert gas.

It is an object of the present invention to provide a process for preparing an improved aliphatic or semiaromatic polyamide. This is characterized by advantageous product properties, more specifically not too broad a molecular weight distribution and / or low gel content.

Surprisingly, it has been found that this object is achieved when the solid phase polymerization is carried out in a sealed vessel at elevated pressure and in the presence of an inert gas for the prepolymer of aliphatic or semiaromatic polyamides. This is particularly surprising since during solid phase polymerization there may be no release of constituents, in particular water, from the interior of the container into the environment.

The present invention relates to a process for producing an aliphatic or semiaromatic polyamide,

a) providing a prepolymer of an aliphatic or semiaromatic polyamide,

b) subjecting the prepolymer provided in step a) to solid phase polymerization in a closed vessel under elevated temperature and elevated pressure in the presence of an inert gas under process conditions.

The present invention further provides an aliphatic or semiaromatic polyamide obtainable by the process as defined above and below.

The present invention further provides a polyamide molding composition comprising at least one polyamide obtainable by the process defined above and below. The present invention further provides moldings made from such polyamide molding compositions.

The present invention further provides the use of aliphatic polyamides obtainable by the methods defined above and below, for the production of films, monofilaments, fibers, yarns or textile fabrics.

The present invention further provides uses for semiaromatic polyamides obtainable by the processes defined above and below, preferably for the production of electrical and electronic components and for applications in high temperature automotive applications.

"Solid phase polymerization" is understood to mean a condensation reaction which increases the molecular weight generally within the range of the glass transition temperature of the polyamide to the melting point or lower. Within this temperature range, unwanted thermal decomposition of the polyamide can be substantially avoided.

"Solid phase polymerization in a closed vessel" is understood to mean that no mass transfer occurs between the interior of the vessel and the environment after the polymerization temperature is obtained. More specifically, the gas stream does not pass through the vessel during the solid state polymerization. Thus, during solid phase polymerization, there is no release of constituents, e.g. water, from the interior of the container to the environment. In the solid phase polymerization of the present invention in a closed vessel, heat exchange between the interior of the vessel and the environment is allowed in contrast.

In the context of the present invention, a prepolymer refers to a composition comprising a polymeric compound having a complementary functional group capable of a condensation reaction to increase molecular weight.

Condensation of monomers of an acid component and a diamine component, and also any lactam component used, forms a repeating unit or terminal group in the form of an amide derived from each monomer. These monomers generally amount to 95 mol%, especially 99 mol%, of all repeating units and terminal groups present in the copolyamide. In addition, copolyamides may also contain small amounts of other repeating units that may result from the decomposition or side reactions of monomers, such as diamines.

Polyamides are designated in the context of the present invention using the abbreviations, some of which are conventional in the art, and these are the letters PA followed by numbers and letters. Some of these codes are standardized in DIN EN ISO 1043-1. Aminocarboxylic acids in the form of H ₂ N- (CH ₂ ) _x -COOH or polyamides which may be derived from the corresponding lactam are identified as PA Z, wherein Z represents the number of carbon atoms in the monomers. For example, PA 6 represents a polymer of? -Caprolactam or? -Aminocaproic acid. Polyamides derived from diamines and dicarboxylic acids in the form of H ₂ N- (CH ₂ ) _x -NH ₂ and HOOC- (CH ₂ ) _y -COOH are identified as PA Z1Z2 where Z1 is the number of carbon atoms in the diamine And Z2 represents the number of carbon atoms in the dicarboxylic acid. Copolyamides are designated by listing the components as a series of these ratios separated by slashes. For example, PA 66/610 is a copolyamide of hexamethylenediamine, adipic acid and sebacic acid. For monomers with aromatic or alicyclic groups used according to the invention, the following letter designations are used: T = terephthalic acid, I = isophthalic acid, MXDA = m-xylenediamine, IPDA = isophoronediamine, PACM = '-Methylenebis (cyclohexylamine), MACM = 2,2'-dimethyl-4,4'-methylenebis (cyclohexylamine).

Hereafter, the expression "C ₁ -C ₄ -alkyl" includes unsubstituted straight and branched C ₁ -C ₄ -alkyl groups. Examples of C ₁ -C ₄ -alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl (1,1-dimethylethyl).

In the aromatic dicarboxylic acid, the aliphatic dicarboxylic acid, the alicyclic dicarboxylic acid and the monocarboxylic acid which will be mentioned later, the carboxyl groups may each be present in the non-dihydrogenated form or in the form of derivatives. In the case of a dicarboxylic acid, either the carboxyl group may not be in the form of a derivative, or one carboxyl group or both carboxyl groups may be present in the form of a derivative. Suitable derivatives are anhydrides, esters, acid chlorides, nitriles and isocyanates. Preferred derivatives are anhydrides or esters. The anhydrides of dicarboxylic acids may be in monomeric form or in polymeric form. Preferred esters are alkyl esters and vinyl esters, more preferably C ₁ -C ₄ -alkyl esters, especially methyl esters or ethyl esters. The dicarboxylic acid is preferably a mono- or dialkyl ester, more preferably a mono- or di-C ₁ -C ₄ -alkyl ester, more preferably a monomethyl ester, dimethyl ester, monoethylacetate or diethyl It is in the form of esters. The dicarboxylic acid is further preferably in the form of a mono- or divinyl ester. The dicarboxylic acid is further preferably in the form of a mixed ester, more preferably a mixed ester in which the C ₁ -C ₄ -alkyl component is different, in particular methylethylester.

A prepolymer is obtained by polycondensation of an aqueous composition comprising at least one component suitable for polyamide formation.

Preferably, the prepolymer (and thus the aliphatic or semiaromatic polyamide)

A) a derivative of an unsubstituted or substituted aromatic dicarboxylic acid and an unsubstituted or substituted aromatic dicarboxylic acid,

B) an unsubstituted or substituted aromatic diamine,

C) aliphatic or alicyclic dicarboxylic acids and their derivatives,

D) an aliphatic or alicyclic diamine,

E) monocarboxylic acids and derivatives thereof,

F) monoamine,

G) at least a trifunctional amine,

H) lactam,

I) omega-amino acid,

K) a compound which is different from A) to I) and is capable of co-

≪ / RTI >

A suitable embodiment is an aliphatic polyamide. For an aliphatic polyamide of the PA Z1Z2 form (e.g. PA 66), the conditions are such that at least one of the components C) and D) must be present and that none of the components A) and B) can be present. For an aliphatic polyamide of the PA Z form (e.g. PA 6 or PA 12), the proviso that at least component H) is present is applied.

A preferred embodiment is a semi-aromatic polyamide. For semiaromatic polyamides, the proviso that at least one of the components A) and B) and at least one of the components C) and D) must be present.

Aromatic dicarboxylic acid A) is preferably in each case unsubstituted or substituted phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or diphenyl dicarboxylic acid, and the above-mentioned aromatic dicarboxylic acid Derivatives and mixtures thereof.

The substituted aromatic dicarboxylic acids A) preferably have at least one, for example 1, 2, 3 or 4, C ₁ -C ₄ -alkyl radicals. More specifically, the substituted aromatic dicarboxylic acid A) has 1 or 2 C ₁ -C ₄ -alkyl radicals. These are preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, more preferably methyl, ethyl and n- , Especially methyl. Substituted aromatic dicarboxylic acids A) may also have further functional groups which do not destroy amidation, such as 5-sulfoisophthalic acid, and salts and derivatives thereof. A preferred example thereof is the sodium salt of dimethyl 5-sulfoisophthalate.

Preferably, the aromatic dicarboxylic acid A) is selected from the group consisting of unsubstituted terephthalic acid, unsubstituted isophthalic acid, unsubstituted naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5- ≪ / RTI > sulfoisophthalic acid.

More preferably, the aromatic dicarboxylic acid A) used is terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.

Preferably, the proportion of the aromatic dicarboxylic acid in all dicarboxylic acids is at least 50 mol%, more preferably 70 mol% to 100 mol%, in the semiaromatic polyamide prepolymer provided according to the present invention. In a specific embodiment, the semiaromatic polyamide prepared by the process according to the invention (and the prepolymer provided in step a)) is such that the ratio of terephthalic acid or isophthalic acid or a mixture of terephthalic acid and isophthalic acid is higher than that of all dicarboxylic acids At least 50 mol%, preferably 70 mol% to 100 mol%.

Aromatic diamine B) is preferably selected from the group consisting of bis (4-aminophenyl) methane, 3-methylbenzidine, 2,2-bis (4-aminophenyl) propane, Diaminobenzene, 1,4-diaminobenzene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,3-diaminotoluene (s), m-xylenediamine, N, N (4-methylaminophenyl) methane, 2,2-bis (4-methylaminophenyl) -propane or mixtures thereof.

Aliphatic or alicyclic dicarboxylic acid C) is preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- Dicarboxylic acid, fumaric acid or itaconic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1 Dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans- 1,3-dicarboxylic acid, and mixtures thereof.

The aliphatic or alicyclic diamine D) is preferably selected from the group consisting of ethylenediamine, propylenediamine, tetramethylenediamine, heptamethylenediamine, hexamethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, Methylene diamine, methylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, Methylene diamine, 2,4-dimethyloctamethylene diamine, 5-methyl nonanediamine, bis (4-aminocyclohexyl) methane, 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane, .

More preferably, the diamine D) is at least one selected from the group consisting of hexamethylene diamine, 2-methylpentamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, bis (4-aminocyclohexyl) Methane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, and mixtures thereof.

In a specific embodiment, the semiaromatic polyamides include hexamethylenediamine, bis (4-aminocyclohexyl) methane (PACM), 3,3'-dimethyl- Diamine (IPDA), and mixtures thereof.

In a specific embodiment, the semiaromatic polyamide comprises only hexamethylenediamine as the copolymerized diamine D).

In a further specific embodiment, the semiaromatic polyamide comprises only bis (4-aminocyclohexyl) methane as the copolymerized diamine D).

In a further specific embodiment, the semiaromatic polyamide comprises only 3,3'-dimethyl-4,4'-diaminocyclohexylmethane (MACM) as the copolymerized diamine D).

In a further specific embodiment, the semiaromatic polyamide comprises only isophoronediamine (IPDA) as the copolymerized diamine D).

The prepolymer (and the corresponding aliphatic and semiaromatic polyamides) may comprise at least one copolymerized monocarboxylic acid E). Monocarboxylic acid E) helps to end-cap polyamides prepared according to the present invention. Suitable monocarboxylic acids are in principle all monocarboxylic acids capable of reacting with at least some of the available amino groups under the reaction conditions of polyamide condensation. Suitable monocarboxylic acids E) are aliphatic monocarboxylic acids, alicyclic monocarboxylic acids and aromatic monocarboxylic acids. These may be selected from acetic acid, propionic acid, n-, iso- or tert-butyric acid, valeric acid, trimethylacetic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, Naphthalenecarboxylic acid, p-naphthalenecarboxylic acid, phenylacetic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, stearic acid, fumaric acid, It includes linolenic acid, erucic acid, soybean, linseed, castor oil plants, and fatty acids from sunflower, acrylic acid, methacrylic acid, Versatic acid ^{®, ®} Koch acid, and mixtures thereof.

If the monocarboxylic acid E) used is an unsaturated carboxylic acid or derivative thereof, it is advisable to work in the presence of a commercial polymerization inhibitor.

More preferably, the monocarboxylic acid E) is selected from acetic acid, propionic acid, benzoic acid, and mixtures thereof.

In a specific embodiment, the prepolymer (and the corresponding aliphatic and semiaromatic polyamides) comprise only propionic acid as the copolymerized monocarboxylic acid E).

In a further specific embodiment, the prepolymer (and the corresponding aliphatic and semiaromatic polyamides) comprise only benzoic acid as the copolymerized monocarboxylic acid E).

In a further specific embodiment, the prepolymer (and the corresponding aliphatic and semiaromatic polyamides) comprise only acetic acid as the copolymerized monocarboxylic acid E).

The prepolymer (and the corresponding aliphatic and semiaromatic polyamides) may comprise at least one copolymerized monoamine F). In this context, the aliphatic polyamides include only copolymerized aliphatic monoamines or cycloaliphatic monoamines. Monoamine F) helps to end-cap polyamides prepared according to the present invention. Suitable monoamines are in principle all monoamines capable of reacting with at least some of the available carboxyl groups under the reaction conditions of polyamide condensation. Suitable monoamines F) are aliphatic monoamines, alicyclic monoamines and aromatic monoamines. These may be selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine , Dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine, and mixtures thereof.

For the preparation of prepolymers (and corresponding aliphatic and semiaromatic polyamides) it is also possible to use at least one further at least one trifunctional amine G). These include, but are not limited to, N '- (6-aminopentyl) -hexane-1,6-diamine, N' - (12-aminododecyl) dodecane-1,12- Diamine, N '- [3- (aminomethyl) -3,5-trimethylcyclohexyl] hexane-1,6-diamine, Diaminocyclohexyl] dodecane-1,12-diamine, N '- [(5-amino-1,3,3-trimethylcyclohexyl) methyl] hexane- Amino] -1,3,3-trimethylcyclohexyl) methyl] dodecane-1,12-diamine, 3 - [[[3- (aminomethyl) -3,5,5- trimethylcyclohexyl] Trimethylcyclohexaneamine, 3 - [[(5-amino-1,3,3-trimethylcyclohexyl) methylamino] methyl] -3,5,5-trimethylcyclohexaneamine, 3- (Aminomethyl) -N- [3- (aminomethyl) -3,5,5-trimethylcyclohexyl] -3,5,5-trimethylcyclohexaneamine. Preferably, at least a trifunctional amine G) is not used.

Suitable lactams H) include, but are not limited to, ε-caprolactam, 2-piperidone (δ-valerolactam), 2-pyrrolidone (γ-butyrolactam), caprylactam, enantholactam, lauryllactam, to be.

Suitable ω-amino acids I) are 6-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof.

Suitable compounds K) which are different from A) to I) and are co-condensable therewith are at least tribasic carboxylic acids, diaminocarboxylic acids and the like.

Suitable compounds K) are furthermore 4 - [(Z) -N- (6-aminohexyl) -C- hydroxycarbonimidoyl] benzoic acid, 3 - [(Z) - (hydroxycarbonimidoyl) benzoic acid, (6Z) -6- (6-aminohexylamino) -6-hydroxyhexanecarboxylic acid, 4- [ 3 - [(Z) -N - [(5-amino-1,3,3-trimethylcyclohexyl) methyl] - C - [(Z) -N- [3- (aminomethyl) -3,5,5-trimethylcyclohexyl] -C- hydroxycarbonimidoyl] benzoic acid, 3- [ (Z) -N- [3- (aminomethyl) -3,5,5-trimethylcyclohexyl] -C-hydroxycarbonimidoyl] benzoic acid and mixtures thereof.

In a preferred embodiment, the process according to the invention is useful for the production of aliphatic polyamides.

In this case, the polyamide is preferably PA 6, PA 11, PA 12, PA 46, PA 66, PA 666, PA 69, PA 610, PA 612, PA 96, PA 99, PA 910, PA 912, PA 1212, and copolymers and mixtures thereof.

More specifically, the aliphatic polyamide is PA 6, PA 66 or PA 666, and most preferably PA 6.

In a further preferred embodiment, the process according to the invention is useful for the preparation of semi-aromatic polyamides.

In this case, the polyamide is preferably selected from PA 6.T, PA 9.T, PA 8.T, PA 10.T, PA 12.T, PA 6.I, PA 8.I, PA 9.I, PA 10.I, PA 12.I, PA 6.T / 6, PA 6.T / 10, PA 6.T / 12, PA 6.T / 6.I, PA 6.T / 8.T, PA 6 6.T / 10T, PA 6.T / 12.T, PA 12.T / 6.T, PA 6.T / 6.I / 6, PA 6.T / 6. I / 12, PA 6.T / 6.I / 6.10, PA 6.T / 6.I / 6.12, PA 6.T / 6.6, PA 6.T / 6.10, PA 6.T / 6.12, PA 10. T / 6, PA 10.T / 11, PA 10.T / 12, PA 8.T / 6.T, PA 8.T / 66, PA 8.T / 8.I, PA 8.T / 8.6, PA 10.T / 6.I, PA 10.T / 6.T, PA 10.T / 6.6, PA 10.T / 10.I, PA 10T / 10.I / 6.I, PA 4.T / 4.I / 46, PA 4.T / 4.I / 6.6, PA 5.T / 5.I, PA 5.T / 5.I / 5.6, PA 5.T / PA.I / 6.6, PA 6.T / 6.I / 6.6, PA MXDA.6, PA IPDA.I, PA IPDA.T, PA MACM.I, PA MACM.T, PA PACM.I, PA PACM / RTI > 6.T / IPDA.T, PA 6.T / MACM.T, PA 6.T / PACM.T, PA 6.T / MXDA.T, PA MXDA.I, 6.T / 6.I / 8.T / 8.I, PA 6.T / 6.I / 10.T / 10.I, PA 6.T / 6.I / IPDA.T / IPDA.I, PA 6.T / 6.I / MXDA.T / MXDA.I, PA 6.T / 6.I / MACM.T / MACM.I, PA 6.T / 6.I / PACM.T / PACM.I , PA 6.T / 10.T / IPDA.T, PA 6.T / 12.T / IPDA.T, PA 6.T / 10.T / PACM.T, PA 6.T / 12.T / PACM .T, PA 10.T / IPDA.T, P A 12. T / IPDA.T, and copolymers and mixtures thereof.

In this case, the polyamide is more preferably PA 6.T, PA 9.T, PA 10.T, PA 12.T, PA 6.I, PA 9.I, PA 10.I, PA 12.I , PA 6.T / 6.I, PA 6.T / 6.T, PA 6.T / 8.T, PA 6.T / 10T, PA 10.T / PA12.T / 6.T, PA IPDA.I, PA IPDA.T, PA 6.T / IPDA.T, PA 6.T / 6.I / IPDA.T / IPDA.I, PA 6.T / 10 / RTI > T / IPDA.T, PA 6.T / 12.T / IPDA.T, PA 6.T / 10.T / PACM.T, PA 6.T / 12.T / PACM.T, PA 10.T / IPDA.T, PA 12.T / IPDA.T, and copolymers and mixtures thereof.

In a specific embodiment, the semiaromatic polyamide is PA 6.T / 6.I.

In a further specific embodiment, the semiaromatic polyamide is PA 6.T / 6.I / IPDA.T / IPDA.I.

In a further specific embodiment, the semiaromatic polyamide is PA 6.T / 6.I / MXDA.T / MXDA.I.

For the preparation of the prepolymers provided according to the invention, aqueous compositions comprising at least one component suitable for polyamide formation are generally used. The prepolymers can in principle be prepared by conventional processes known to those skilled in the art.

Suitable methods for preparing the semi-aromatic polyamide oligomers are described, for example, in European Patent Application No. 0 693 515 A1.

The aqueous composition used in the preparation of the prepolymer is preferably 20 to 55% by weight, more preferably 25 to 50% by weight, based on the total weight of the composition. In a specific embodiment, there is provided an aqueous solution comprising a salt of at least one diamine and at least one carboxylic acid. The solution preferably has a water content of 20 to 55% by weight, more preferably 25 to 50% by weight, based on the total weight of the solution.

In addition to one or more components and water suitable for polyamide formation, the aqueous composition used in the preparation of the prepolymer may contain additional components. These are preferably selected from catalysts, chain transfer agents, application-related additives and mixtures thereof. Suitable additives include flame retardants, inorganic and organic stabilizers, lubricants, dyes, nucleating agents, metal pigments, metal flakes, metal coated particles, antistatic agents, conductive additives, release agents, optical brighteners, defoamers, fillers and / or reinforcers.

For the preparation of the prepolymer, it is possible to use at least one catalyst. Suitable catalysts are preferably selected from inorganic and / or organic phosphorus, tin or lead compounds, and mixtures thereof.

Examples of suitable tin compounds as catalysts are tin (II) oxides, tin (II) hydroxide, tin (II) salts such as tin (II) dibenzoate, tin (II) oxide of monobasic or polybasic carboxylic acids, Di (2-ethylhexanoate), tin (II) oxalate, dibutyltin oxide, butyltin acid (C ₄ H ₉ -SnOOH), dibutyltin dilaurate and the like. Suitable lead compounds are, for example, lead (II) oxide, lead (II) hydroxide, lead (II) acetate, basic lead (II) acetate, lead (II) carbonate and the like.

Preferred catalysts are phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid and / or mono- to trivalent cations such as Na, K, Mg, Ca, Zn or Al and their salts And / or their esters, such as triphenyl phosphate, triphenyl phosphite or phosphorous tris (nonylphenyl). Particularly preferred catalysts are hypophosphorous acid and its salts, for example sodium hypophosphite.

The catalyst is preferably used in an amount of from 0.005 to 2.5% by weight, based on the total weight of the aqueous composition.

It is particularly advantageous to use hypophosphorous acid and / or hypophosphite in an amount of 50 to 1000 ppm, more preferably 100 to 500 ppm, based on the total amount of components (= components A) to K) suitable for polyamide formation desirable.

The ring-opening lactam polymerization can be carried out by pure hydrolysis without the use of a catalyst. In the case of activated anion lactam polymerization, a catalyst is used which enables the formation of a lactam anion. Suitable catalysts and activators are known to those skilled in the art. The preparation of polyamide-6 from polycondensation of aminonitrile, for example 6-aminocapronitrile (ACN), can be carried out in the presence of a heterogeneous catalyst, for example TiO ₂ .

For controlling the molar mass, it is possible to use at least one chain transfer agent. Suitable chain transfer agents are the monocarboxylic acids A) and monoamines F) mentioned above in a component suitable for polyamide formation. The chain transfer agent is preferably selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3- Hydroxyphenyl) propanoic acid, 3- (3-tert-butyl-4-hydroxyphenyl) propanoic acid, 3,5-di-tert- (3-tert-butyl-4-hydroxyphenyl) butanoic acid, butylamine, pentylamine, hexylamine, 2-tert- butyl-4-hydroxybenzylthio) acetic acid, But are not limited to, ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, 3- (cyclohexylamino) propylamine, methylcyclohexylamine, Dimethylcyclohexylamine, benzylamine, 2-phenylethylamine, 2,2,6,6-tetramethylpiperidin-4-amine, 1,2,2,6,6-pentamethylpiperidine-4- Amine, 4-amino-2,6-di-tert-butylphenol, and mixtures thereof. It is also possible to use other monofunctional compounds, such as anhydrides, isocyanates, acid halides or esters, which can react with amino groups or acid groups as transfer agents. The usual amount of chain transfer agent is in the range of 5 to 500 mmol per kg of prepolymer, preferably 10 to 200 mmol per kg of polyamide oligomer.

If desired, additional additives may be added to the aqueous composition, such as catalysts and chain transfer agents. Additives include, for example, antioxidants, light stabilizers, standard processing aids, nucleating agents and crystallization promoters.

The prepolymer that is provided is preferably the number average molecular weight M _n of about 500~ about 12000 g / mol, preferably from about 1000~4000 g / mol.

The prepolymer provided in step a) may be provided in a particle size ranging from fine particle to granule size range. Preferably, the prepolymer provided in step a) has a particle size in the range of 1 [mu] m to 10 mm. A preferred embodiment is a powder having a particle size in the range of 100 [mu] m to 1 mm.

Preferably, molding is carried out before being used in step b) for the prepolymer. Preferably, the shaping of the prepolymer comprises pelletizing and / or grinding operations. Suitable processes for pelleting and milling polyamides are known to those skilled in the art. Suitable processes are described, for example, in Kunststoffhandbuch, 3/4 Technische Thermoplaste: Polyamide, Carl Hanser Verlag, 1998, Munich, p. 68-69. The specific shaping process is likewise in principle an underwater pelletization known to those skilled in the art. In a suitable embodiment, the polyamide is first shaped into at least one strand for forming. For this purpose, devices known to those skilled in the art can be used. Suitable devices are, for example, apertured plates, nozzles or die plates. The strand diameter is preferably in the range of 0.5 mm to 20 mm, more preferably in the range of 1 mm to 5 mm, and most preferably in the range of 1.5 mm to 3 mm. In a preferred embodiment, the strand-shaped polyamide is pulverized in free-flowing form to provide polyamide particles. In an alternative embodiment, the strand-shaped polyamide is solidified and then ground to provide polyamide particles. Suitable mills for grinding prepolymers are, for example, hammer mills, roll mills, ball mills and the like.

In step b) of the process according to the invention, the prepolymer provided in step a) is subjected to solid phase polymerization in a closed vessel at elevated temperature and elevated pressure in the presence of a gas inert under the treatment conditions.

Closed containers suitable for solid state polymerization are pressure vessels (autoclaves) which are known to those skilled in the art and which can be hermetically sealed, as is commonly used in the heat treatment of materials at elevated pressures.

In the solid phase polymerization in step b), the temperature in the closed vessel is preferably in the range of 200 to 290 캜, more preferably in the range of 250 to 280 캜.

In the solid phase polymerization in step b), the pressure in the sealed vessel is preferably in the range from 1.5 to 20 bar, more preferably from 2 to 15 bar, especially from 3 to 10 bar. A particularly suitable pressure range is 4 to 7 bar.

The residence time in step b) in the closed vessel is preferably 0.5 to 72 hours, more preferably 1 to 48 hours, particularly 2 to 24 hours.

Suitable inert gases are, for example, nitrogen, CO ₂ , helium, neon and argon, and mixtures thereof. It is preferable to use nitrogen.

A semiaromatic polyamide having properties particularly advantageous in the process according to the invention is obtained.

In the context of the present invention, the values for the number average molecular weight M _n and the weight average molecular weight M _w are respectively based on measurements by gel permeation chromatography (GPC). For calibration, PMMA was used as a low polydispersity polymer standard.

The polyamide obtained by the process according to the invention, aliphatic polyamide, and the present invention is preferably in a number average molecular weight M _n is 13,000 to 28,000 g / mol range.

Is within the present invention, semi-aromatic polyamide, and a polyamide obtained by the method according to the invention preferably has a number average molecular weight M _n is 13,000 to 25,000 g / mol, more preferably from 15,000 to 20,000 g / mol range.

The inventive aliphatic polyamides and the polyamides obtained by the process according to the invention preferably have a weight average molecular weight M _w in the range from 20,000 to 140,000 g / mol.

The inventive semiaromatic polyamides and the polyamides obtained by the process according to the invention preferably have a weight average molecular weight M _w in the range from 25,000 to 125,000 g / mol.

The inventive aliphatic and semiaromatic polyamides and the polyamides obtained by the process according to the invention preferably have a polydispersity PD (= M _w / M _n ) of not more than 6, more preferably not more than 5 In particular, not exceeding 3.5.

The aliphatic polyamides obtainable by the process according to the invention are particularly suitable for the production of films, monofilaments, fibers, yarns or textile fabrics. In this context, the aliphatic polyamides produced in accordance with the present invention can be produced by forming a flat film or blown film through a slot die or annular die, and during melt extrusion to form a monofilament through a smaller diameter annular die It is generally known that it is particularly stable in processing.

The semiaromatic polyamides obtainable by the process according to the invention are likewise of advantageous properties.

The inventive semiaromatic polyamides and the polyamides obtained by the process according to the invention preferably have a gel content of not more than 5% by weight, based on the total weight of the polyamides.

The inventive semiaromatic polyamides and the polyamides obtained by the process according to the invention preferably have a viscosity of 80 to 120 ml / g. (Referred to as a star right dinggeo function, VN or J) viscosity number is defined as VN = 1 / cx (η- η s) / η s. The viscosity number is directly related to the average molar mass of the polyamide and provides information on the processability of the polymer. The number of viscosities can be measured according to EN ISO 307 by Ubbelohde viscometer.

Polyamide molding composition

The present invention further provides a polyamide molding composition comprising at least one inventive semiaromatic copolyamide.

As the polyamide molding composition

A) 25 to 100% by weight of at least one semi- aromatic copolyamide as defined above,

B) from 0 to 75% by weight of one or more fillers and reinforcing agents,

C) from 0 to 50% by weight of at least one additive,

Here, the components A) to C) together are preferably 100% by weight in total of the polyamide molding composition.

The term "filler and reinforcing agent" (= component B) is understood in the context of the present invention in a broad sense and includes particulate fillers, fibrous materials and any intermediate forms. Particulate fillers can have a wide range of particle sizes, from dust-like particles to large granules. Useful filler materials include organic or inorganic fillers and reinforcing agents. For example, inorganic fillers such as kaolin, chalk, wollastonite, talc, calcium carbonate, silicates, titanium dioxide, zinc oxide, graphite, glass particles such as glass beads, nanoscale fillers such as carbon nanotubes , carbon black, nano-scale phyllosilicates, nanoscale alumina (Al ₂ O _3), nanoscale titania (TiO _2), graphene (graphene), permanently magnetic or magnetized metal compound and / or alloy, the layer silicate and nanoscale It is possible to use silica (SiO ₂ ). Fillers can also be surface treated.

Examples of layered silicates used in the molding compositions of the present invention include kaolin, serpentine, talc, mica, vermiculite, ilite, smectite, montmorillonite, hectorite, bicarbonate or mixtures thereof. The layered silicate may or may not be surface treated.

In addition, it is possible to use one or more fibrous materials. These are preferably inorganic known reinforcing fibers such as boron fibers, glass fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers; Organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.

It is particularly preferable to use glass fibers, carbon fibers, aramid fibers, boron fibers, metal fibers or potassium titanate fibers.

Particularly, fine fiberglass is used. More specifically, component B) comprises glass fibers and / or carbon fibers, preferably using short fibers. They are preferably in the range of 2 to 50 mm in length and 5 to 40 탆 in diameter. Alternatively, it is possible to use continuous fibers (crude yarn). Suitable fibers are fibers whose cross-sectional area is circular and / or non-circular, and in the latter case the aspect ratio of the major cross-sectional axis to the minor cross-sectional axis is in particular > 2, preferably in the range of 2 to 8, more preferably in the range of 3 to 5.

In a specific embodiment, component B) comprises so-called "flat glass fibers ". They are specifically oval or elliptical or elliptical and have indent (s) (referred to as "cocoon " fibers), or have a cross-sectional area that is rectangular or substantially rectangular. Here, it is preferable to use a glass fiber having a non-circular cross-sectional area and a dimensional ratio of the main section axis to the auxiliary section axis of more than 2, preferably 2 to 8, especially 3 to 5.

In order to strengthen the molding composition of the present invention, it is also possible to use a mixture of glass fibers having a circular and non-circular cross-section. In a specific implementation, the proportion of flat glass fibers as defined above is predominant, meaning that they constitute more than 50% by weight of the total fiber mass.

When the glass fibers are used as component B), they preferably have a diameter of from 10 to 20 mu m, preferably from 12 to 18 mu m. In this case, the cross section of the glass fibers may be round, oval, elliptical, substantially rectangular or rectangular. So-called flat glass fibers with a ratio of cross-sectional axes of 2 to 5 are particularly preferred. More specifically, E glass fiber is used. However, it is also possible to use all other glass fiber forms, for example A, C, D, M, S or R glass fibers or any desired mixtures thereof, or E glass fibers and mixtures.

The polyamide molding composition of the present invention can be produced by a process for the production of known long fiber reinforced rod pellets, in particular by a draw-forming process wherein the continuous fiber strand (crude spinning) is fully saturated with the polymer melt and then cooled and cut. The long fiber reinforced rod pellets obtained in this way, preferably having a pellet length of from 3 to 25 mm, in particular from 4 to 12 mm, can be processed by conventional processing methods, for example injection molding or press molding, have.

The polyamide molding composition of the present invention preferably comprises 25 to 75 wt%, more preferably 33 to 60 wt% of one or more fillers or reinforcing agents B) based on the total weight of the polyamide molding composition.

Suitable additives C) may be selected from the group consisting of heat stabilizers, flame retardants, light stabilizers (UV stabilizers, UV absorbers or UV screening agents), lubricants, dyes, nucleators, metal pigments, metal flakes, metal coating particles, antistatic agents, A release agent, an optical brightener, a defoaming agent, and the like.

As component C), the molding compositions of the present invention preferably comprise from 0.01 to 3% by weight, more preferably from 0.02 to 2% by weight, in particular from 0.1 to 1.5% by weight, of at least one heat stabilizer.

The heat stabilizer is preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof.

When a copper compound is used, the amount of copper is preferably 0.003 to 0.5% by weight, particularly 0.005 to 0.3% by weight, more preferably 0.01 to 0.2% by weight, based on the total of components A) to C).

When stabilizers based on secondary aromatic amines are used, the amount of these stabilizers is preferably from 0.2 to 2% by weight, more preferably from 0.2 to 1.5% by weight, based on the sum of components A) to C).

When a stabilizer based on a sterically hindered phenol is used, the amount of these stabilizers is preferably from 0.1 to 1.5% by weight, more preferably from 0.2 to 1% by weight, based on the sum of components A) to C).

When stabilizers based on phosphites and / or phosphonites are used, the amount of these stabilizers is preferably from 0.1 to 1.5% by weight, more preferably from 0.2 to 1% by weight, based on the sum of components A) to C) Weight%.

Suitable compounds C) of monovalent or divalent copper are, for example, salts of inorganic or organic acids or mono- or dihydric phenols with mono- or di-valent copper, mono- or divalent copper or with ammonia, amines, amides, A complex of a lactam, cyanide or phosphine with a copper salt, preferably a Cu (I) or Cu (II) salt of a hydrohalic acid or hydrocyanic acid or a copper salt of an aliphatic carboxylic acid. Particularly preferred are monovalent copper compounds CuCl, CuBr, CuI, CuCN and Cu ₂ O, and divalent copper compounds CuCl ₂ , CuSO ₄ , CuO, copper (II) acetate or copper (II) stearate.

Copper compounds are commercially available, or the preparation thereof is known to those skilled in the art. The copper compound can be used as it is or in the form of a concentrate. The concentrate is understood to mean a polymer of the same chemical nature as component A), preferably containing a high concentration of copper salt. The use of concentrates is standard practice and is used particularly frequently when very small amounts of feedstock are to be weighed. Advantageously, the copper compound is used in combination with further metal halides, especially alkali metal halides such as NaI, KI, NaBr, KBr, in which case the molar ratio of metal halide to copper halide is from 0.5 to 20 , Preferably 1 to 10, more preferably 3 to 7.

Particularly preferred examples of stabilizers which are based on secondary aromatic amines and which can be used according to the invention are adducts of acetone with phenylenediamine (Naugard A), adducts of linolenic acid with phenylenediamine, 4,4'-bis phenylenediamine, N, N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p- / RTI >

Preferred examples of stabilizers based on sterically hindered phenols and usable according to the invention are N, N'-hexamethylenebis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide , Bis (3,3-bis (4'-hydroxy-3'-tert-butylphenyl) butanoic acid) glycol ester, 2,1'-thioethyl bis (3- (3,5- Butylphenyl) propionate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl), triethylene glycol 3- (3- 5-methylphenyl) propionate or a mixture of two or more of these stabilizers.

Preferred phosphites and phosphonites include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythrityl diphosphite, (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di- 4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra -tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra- (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tert- butyl) -6-methylphenyl) ethyl phosphite. More specifically, it is possible to use tris [2- tert -butyl-4-thio (2'-methyl-4'-hydroxy-5'- (Di-tert-butylphenyl) phosphite (Hostanox (R) PAR24 (commercially available from BASF SE) is preferred.

Preferred embodiments of heat stabilizers are in combination with organic thermal stabilizers (especially Hostanox PAR 24 and Irganox 1010), bisphenol A based epoxides (especially Epikote 1001) and copper stabilizations based on CuI and KI. An example of a commercial stabilizer mixture consisting of an organic stabilizer and an epoxide is Irgatec NC66 from BASF. More specifically, thermal stabilization based on CuI and KI is preferred. Apart from the use of copper or copper compounds, the use of additional transition metal compounds, in particular metal salts or metal oxides of the Periodic Table VB, VIB, VIIB or VIIIB groups, is excluded. It is also preferred that no transition metal, such as iron or steel, of the periodic table VB, VIB, VIIB or VIIIB is added to the molding composition of the present invention.

The inventive molding composition preferably comprises 0 to 30% by weight, more preferably 0 to 20% by weight, of one or more flame retardants as additives C), based on the total weight of components A) to C). When the molding composition of the present invention comprises at least one flame retardant, they are preferably contained in an amount of 0.01 to 30% by weight, more preferably 0.1 to 20% by weight, based on the total weight of components A) to C). Useful flame retardants C) include halogenated and halogen-free flame retardants and their synergists (see also Gaechter / Mueller, 3rd edition 1989 Hanser Verlag, chapter 11). Preferred halogen-free flame retardants are selected from the group consisting of rubbers, phosphinates or diphosphates and / or nitrogen containing flame retardants such as melamine, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, melamine phosphate (primary, secondary) Melamine pyrophosphate, neopentyl glycol boric acid melamine, guanidine and derivatives thereof known to those skilled in the art, and also polymeric melamine phosphate (CAS No. 56386-64-2 or 218768-84-4, 1095030), ammonium polyphosphate, trishydroxyethylisocyanurate (optionally also ammonium polyphosphate as a mixture with trishydroxyethylisocyanurate) (EP 584567). N-containing or P-containing flame retardants, or PN condensates suitable as flame retardants can also be found in German Patent No. 10 2004 049 342, which may be analogous to elevators customary for this purpose, such as oxides or borates. Suitable halogenated flame retardants include, for example, oligomeric brominated polycarbonate (BC 52 Great Lakes) or polypentabromobenzyl acrylate with N greater than 4 (FR 1025 Dead sea bromine), reaction of epoxide with tetrabromobisphenol A Products, brominated oligomers or polymer styrenes, dechlorane, which are commonly used with antimony oxides as synergists (see German Patent Application No. 10 2004 050 025 for details and additional flame retardants).

The antistatic agent used in the molding composition of the present invention may be, for example, carbon black and / or carbon nanotubes. The use of carbon black can also help to improve the blackness of the molding composition. However, the molding composition may also contain no metallic pigment.

molding

The present invention further relates to a molding made using the copolyamide or polyamide molding composition of the present invention.

The inventive semiaromatic polyamides are advantageously suitable for use in the production of moldings for electrical and electronic components and for use in high temperature automotive applications.

Particular embodiments include in particular a cylinder head cover, an engine hood, a housing for an air supply chiller, an air supply chiller valve, a suction pipe, a suction manifold, a connector, a gear, a fan impeller, a cooling water tank, a housing or housing part for a heat exchanger, A cooling device, a thermostat, a water pump, a heating element, a fixed part, or as a component part of a component.

Additional specific embodiments include electrical or electronic passive or active components of a printed circuit board, components of a printed circuit board, a housing component, a film, or a wire, or as an active component or as a component thereof, more specifically a switch, plug, bushing, Is a molding in the form of, or as part of, a relay, a resistor, a capacitor, a winding or winding body, a lamp, a diode, an LED, a transistor, a connector, a regulator, an integrated circuit (IC), a processor, a regulator, .

The present semi-aromatic polyamides are particularly suitable for the production of plug connectors, microswitches, micro-buttons and semiconductor components, in particular reflector housings of light emitting diodes (LEDs), for use in soldering operations (lead-free soldering) Do.

Specific embodiments are moldings as fixing elements for electrical or electronic components, such as spacers, bolts, fillets, push-in guides, screws and nuts.

Molding in the form of sockets, plug connectors, plugs or bushings, or as parts thereof, is particularly preferred. The molding preferably includes functional elements that require mechanical toughness. Examples of such functional elements are film hinges, snap-in hooks and spring tongues.

Applications available in automotive interiors are for dashboards, steering shaft switches, seat components, head restraints, central consoles, gearbox components and door modules. Applications for automotive exterior trim include door handles, exterior mirror components, windscreen wiper components, For windshield wiper protection housings, grille, roof rails, sunroof frames, engine covers, cylinder head covers, suction pipes, windshield wipers, and exterior bodywork parts.

The possible uses of flow-improved polyamides for the kitchen and home sector are the manufacture of kitchen machines, for example for fryers, irons and handles, as well as applications in the garden and leisure sector, Garden fittings and door handles.

The following examples are intended to illustrate but not limit the invention in any way.

Example

Analysis method:

Measurement of molecular weight by GPC:

Standard Water: PMMA

Eluent: Hexafluoroisopropanol + 0.05% Potassium trifluoroacetate

Flow rate: 1 ml / min

Column pressure: preliminary column 7.5 MPa, separation column 75 MPa

Column set: One preliminary column (l = 5 cm), two separation columns (l = 30 cm each)

Detector: DRI (refractive index detector) Agilent 1100

The gel content of the polymer was determined indirectly by GPC. For this purpose, a sample of polyamide was dissolved in hexafluoroisopropanol + 0.05% potassium trifluoroacetate and filtered through a filter with a pore size of 0.2 m (Millipore Millex FG). The concentration of polymer eluted from the GPC was then measured. The gel content was calculated from the difference in theoretical polymer concentration provided by the measured concentration (polymer basis used before filtration) and the amount of polymer used before filtration.

A prepolymer was prepared as described in European Patent Application No. 0 693 515 A1, Examples 9.1 to 9.3.

Claims (18)

As a method for producing an aliphatic or semi-aromatic polyamide,
a) providing a prepolymer of an aliphatic or semi-aromatic polyamide,
b) subjecting the prepolymer provided in step a) to solid-state polymerization in an airtight container at elevated temperature and elevated pressure in the presence of a gas inert under the treatment conditions. The process according to claim 1, wherein the prepolymer provided in step a)
A) a derivative of an unsubstituted or substituted aromatic dicarboxylic acid and an unsubstituted or substituted aromatic dicarboxylic acid,
B) an unsubstituted or substituted aromatic diamine,
C) aliphatic or alicyclic dicarboxylic acids and their derivatives,
D) an aliphatic or alicyclic diamine,
E) monocarboxylic acids and derivatives thereof,
F) monoamine,
G) at least a trifunctional amine,
H) lactam,
I) omega-amino acid,
K) A) to I), and a cocondensable compound
≪ / RTI > The process according to claim 2, wherein for the provision of the prepolymer in step a) one or more of components A) and B) must be present. 4. The polyamide according to any one of claims 1 to 3, wherein the polyamide is PA 6.T, PA 9.T, PA 8. T, PA 10.T, PA 12.T, PA 6.I, PA 8.I PA 6.I / PA, 6.I / PA, 6.T / 12, PA 6.I / 6.T / 6.T, PA 6.T / 10.T, PA 6.T / 10.T, PA 6.T / 10.T, PA 6.T / 6.T / 6.I / 12, PA 6.T / 6.I / 6.10, PA 6.T / 6.I / 6.12, PA 6.T / 6.6, PA 6.T / 6.10, PA 6.T / 6.12, PA 10.T / 6, PA 10.T / 11, PA 10.T / 12, PA 8.T / 6.T, PA 8.T / 66, PA 8.T / 8.I, PA 8.T / 8.6, PA 8.T / 6.I, PA 10.T / 6.T, PA 10.T / 6.6, PA 10.T / 10.I, PA 10T / 10.I / 6.T PA 5.T / 5.I, PA 5.T / 5.I / 6.I, PA 4.T / 4.I / 46, 5.6, PA 5.T / 5.I / 6.6, PA 6.T / 6.I / 6.6, PA MXDA.6, PA IPDA.I, PA IPDA.T, PA MACM.I, PA MACM.T, PA PACM.I, PA PACM.T, PA MXDA.I, PA MXDA.T, PA 6.T / IPDA.T, PA 6.T / MACM.T, PA 6.T / PACM.T, PA 6.T / MMDA.T, PA 6.T / 6.I / 8.T / 8.I, PA 6.T / 6.I / 10.T / 10.I, PA 6.T / 6.I / IPDA. T / IPDA.I, PA 6.T / 6.I / MXDA.T / MXDA.I, PA 6.T / 6.I / MACM.T / MACM.I, PA 6.T / 6.I / PACM / RTI > 6.T / 10.T / IPDA.T, PA 6.T / 12.T / IPDA.T, PA 6.T / 10.T / PACM.T, PA 6.T /12.T/PACM T, PA 10. T / IPDA.T, PA 12. T / IPDA.T, and copolymers and mixtures thereof. 5. The process according to any one of claims 1 to 4, wherein the prepolymer provided in step a) is PA 6.T / 6.I or PA 6.T / 6.I / IPDA.T / IPDA.I or PA 6 T / 6.I / MXDA.T / MXDA.I. 6. Process according to any one of claims 1 to 5, wherein the prepolymer provided in step a) has a number average molecular weight of from 500 to about 12,000 g / mol, preferably from about 1,000 to 4,000 g / mol. 7. The process according to any one of claims 1 to 6, wherein the temperature in the closed vessel in the solid phase polymerization of step b) is in the range of 200 to 290C, preferably 250 to 280C. 8. Process according to any one of claims 1 to 7, wherein the pressure in the sealed vessel in the solid phase polymerization of step b) is in the range 1.5 to 20 bar, preferably 2 to 15 bar, especially 3 to 10 bar. A polyamide obtainable by a process as defined in any one of claims 1 to 8. 10. The method of claim 9, wherein the number average molecular weight M _n of the aliphatic polyamide is 13,000~28,000 g / mol range. 10. The method of claim 9, wherein the number average molecular weight M _n of semi-aromatic polyamide is 13,000~25,000 g / mol, preferably 15,000~20,000 g / mol range. Article according to any one of claims 11, wherein the polydispersity not exceeding the _{PD (= M w / M n} ) is 6, and more preferably not more than 5, in particular not exceeding 3.5 Poly amides. A polyamide molding composition comprising at least one polyamide obtainable by the process defined in any one of claims 9 to 12 or as defined in any one of claims 1 to 8. 14. The method of claim 13,
A) from 25 to 100% by weight of at least one polyamide obtainable by the process defined in any one of claims 9 to 12 or by the process defined in any one of claims 1 to 8,
B) from 0 to 75% by weight of one or more fillers and reinforcing agents,
C) from 0 to 50% by weight of at least one additive
/ RTI >
Wherein the components A) to C) together are 100% by weight in total. A molding produced from a polyamide molding composition according to claim 13 or 14. A method for producing a film, monofilament, fiber, yarn or textile fabric according to any one of claims 9, 10 and 12 or according to any one of claims 1 to 8 Use of aliphatic polyamides obtainable by the process defined in one or more of the preceding claims. Method for the production of electrical and electronic components and for the application of high temperature automotive vehicles according to any one of claims 9, 11 and 12 or according to any one of claims 1 to 8 Lt; RTI ID = 0.0 > polyamides < / RTI > The use according to claim 17 for the manufacture of a plug connector, a microswitch, a micro button and a semiconductor component, in particular a reflector housing of a light emitting diode (LED), in a soldering operation under lead-free conditions (lead-free soldering).